Polymer derivatives for treating metals

ABSTRACT

The invention relates to a composition for the treatment of metal surfaces and to the deposition of metals or metal alloys on plastics surfaces, comprising a) at least one polymer as component A, composed of an amino-containing polymer (component Aa), at least one aromatic compound (component Ab), and, where appropriate, an aldehyde (component Ac); b) water or another solvent suitable for dissolving, dispersing, suspending or emulsifying the polymer, as component B; c) if desired, surface-active compounds, dispersants, suspension media and/or emulsifiers as component C. The invention further relates to a process for the treatment of a metal surface and also to a process for the deposition of metals or metal alloys on a-plastics surface in which the metal or plastics surface is contacted with a polymer (component A). The invention further relates to the use of polymers (component A) for the treatment of metal surfaces and for the deposition of metals or metal alloys on a plastics surface, and to polymers composed of specific components A′a, Ab and A′c.

The invention relates to compositions for treating metal surfaces, toprocesses for treating metal surfaces for corrosion protection, to theuse of polymers for treating metal surfaces, and to polymers suitablefor treating metal surfaces. The invention further relates to acomposition and a process for depositing metals or metal alloys onplastics surfaces.

Metal corrosion poses a problem in the production, processing, and useof articles comprising metals. In order to retard or prevent thecorrosion, therefore, protective films and corrosion inhibitors areused. Whereas a protective film is applied permanently to the metal, acorrosion inhibitor is preferably added to substances, especially liquidmixtures, which would cause or accelerate corrosion were they to comeinto contact with the metal. Both the protective, films and thecorrosion inhibitors may comprise, or be present in the form of,polymers. Particular interest attaches to compositions in-which there isno need to use any toxic chromate. Such compositions are already knownfrom the prior art.

U.S. Pat. No. 4,992,116 describes aqueous, chromium-free compositionsand a process for treating aluminum. These compositions comprisephosphate ions and a compound containing an element from the groupconsisting of Zr, Ti, Hf and Si and based on fluorozirconic,fluorotitanic, fluorohafnic, and fluorosilicic acid. The compositionsfurther comprise a polyphenol obtained by Mannich reaction of an aminewith a compound selected from the group consisting of polyalkenylphenolsand tannins. According to U.S. Pat. No. 4,992,116, aluminum surfacestreated with said compositions match chromium-based compositions foradhesion and corrosion resistance.

WO 92/07973 relates to chromium-free corrosion protectants for treatingaluminum or aluminum alloys, which comprise a water-soluble orwater-dispersible polymer. The compositions of WO 92/07973 comprise anacidic aqueous solution which, in addition to water, comprisesfluorozirconic acid, dispersed SiO2 if desired, a nonaqueous solvent, asurfactant, and 3-(N-C₁₋₄alkyl-N-2-hydroxyethylaminomethyl)-4-hydroxystyrene. According to WO92/07973, these specific compositions are particularly suitable fortreating aluminum surfaces.

DE-A 100 10 758 relates to a process for corrosion-protective treatmentof vehicle bodies or domestic appliances that have at least in part ametallic surface composed to the extent of at least 90% of zinc,aluminum and/or magnesium and/or alloys of these metals with one anotheror with other alloy ingredients. Said process encompasses the cleaning,passivating, and coating of the surfaces. For passivating, an aqueoussolution is used which, in addition to complex fluorides of Ti, Zr, Hf,Si and/or B, contains organic polymers. The organic polymers used arepreferably poly-4-vinylphenol compounds. These polyvinyl compounds areobtainable preferably by condensing a polyvinylphenol with formaldehydeor paraformaldehyde and a secondary organic amine.

In view of the importance and breadth of use of corrosion inhibitors andprotective films for metal surfaces there is a great demand forprotective films and corrosion inhibitors whose spectrum of properties,such as adhesion to the metal surface, inhibiting activity, andhydrophobic character, satisfies the stringent requirements with whichthe treated metal surfaces are required to comply. Moreover, thecomponents of the protective films and/or corrosion inhibitors ought tobe easy to obtain in satisfactory quantities and ought to be asinexpensive as possible.

It is an object of the present invention to provide compositions for thesurface treatment of metals resulting in at least one of the followingimprovements to the metal surface: improved corrosion protection,improved adhesion for subsequent enhancement coats (e.g., surfacecoating or metal deposition), passivation, and a smoother surface (inconnection with burnishing, pickling, electropolishing). It is a furtherobject of the present invention to provide processes for the surfacetreatment of metals and of polymers suitable as components for thecompositions of the invention and satisfying the abovementionedrequirements. Furthermore, it is an object of the present invention toprovide additives for the deposition of metals. A further object is toprovide compositions and processes for depositing metals or metal alloyson plastics surfaces.

We have found that these objects are achieved by means of a compositionfor the treatment of metal surfaces, comprising:

-   -   a) at least one polymer as component A, composed of        -   aa) at least one amino-containing polymer as component Aa;        -   ab) at least one aromatic compound as component Ab, being a            phenol or quinone or containing a phenolic or quinonoid            structural unit;        -   ac) if desired, an aldehyde as component Ac;    -   b) water or another solvent suitable for dissolving, dispersing,        suspending or emulsifying the polymer (component A), as        component B;    -   c) if desired, surface-active compounds, dispersants, suspension        media and/or emulsifiers as component C.

This composition of the invention may be used in all processes for metaltreatment, especially those where corrosion of a metal surface mayoccur. Examples of such processes are the passivation, especiallyphosphating, of metal surfaces, preferably chromium-free, the picklingof metal surfaces, the sealing of metal surfaces, and the deposition ofmetal on metal surfaces, by nickeling, zincking, tinning, coppering ordepositing alloy, for example. Furthermore, the compositions may be usedfor producing surface coating materials or rust converters. In theprocesses mentioned, particularly in connection with the passivation ofmetal surfaces and the deposition of metals on metal surfaces, thecompositions comprising the inventively used polymer (component A) bringabout an effective inhibiting action and effective adhesion ofprotective films and/or of an enhancement coat applied over it (e.g., asurface coat or chemically or electrochemically deposited metal coats)to the metal surface. In addition, the compositions of the invention maybe used for depositing metals on plastics surfaces, in the manufactureof printed circuit boards, for example.

The compositions of the invention preferably comprise corrosioninhibitor compositions which are used in processes for the surfacetreatment of metals where corrosion of the metal surface may occur orwhich are intended to prevent corrosion.

Suitable metal surfaces are, in general, common industrial materialsselected from the group consisting of aluminum alloys, magnesium alloys,steel, copper, zinc, tin, nickel, chromium, and common industrial alloysof these metals. Further suitable metal surfaces are precious metals,especially gold and silver and their alloys. Also suitable in generalare common industrial metal coatings which may be produced chemically orelectro-chemically, selected from the group consisting of zinc and itsalloys, preferably metallic zinc, zinc/iron, zinc/nickel, zinc/manganeseor zinc/cobalt alloys, tin and its alloys, preferably metallic tin,alloys of tin containing Cu, Sb, Pb, Ag, Bi, and Zn, with particularpreference those used as solders, in the manufacture and processing ofprinted circuit boards, for example, and copper, preferably in the formin which it is used on printed circuit boards and metallized plasticsparts.

Where the compositions of the invention are used for the pickling orpassivating, especially phosphating, of metal surfaces, the metalsurfaces in question are preferably of steel, cast iron, zinc, aluminum,magnesium and/or alloys of these metals with one another or with otheralloy ingredients. Particular preference is given in such cases to zincand aluminum and to alloys of these metals with other alloy ingredients.

Where the compositions of the invention are used for the deposition ofmetals on metal surfaces, then preference is given to steel surfaceswhen zincking and depositing zinc alloys and also when coppering andnickeling, and to copper and steel when tinning (including Sn alloys).

It is possible to use the composition of the invention for treatingmetal surfaces which have not been pretreated. Preferably, however, themetal surfaces have at least been cleaned prior to treatment with thecomposition of the invention. This cleaning preferably includes, amongother operations, an operation of degreasing the metal surface. Suitablecleaning and degreasing processes are known to the skilled worker. It isalso possible to use the composition of the invention in a process stepfollowing a picking operation or passivating operation on the metalsurface; for example, in a surface coating step. The compositions of theinvention may also be used as cleaning, pickling, and polishingformulations which comprise additives known to the skilled worker andcan be used in corresponding processes.

The compositions of the invention may also be used for the deposition ofmetals or metal alloys on plastics surfaces. The present specificationaccordingly further provides compositions for the deposition of metalson plastics surfaces, comprising:

-   -   a) at least one polymer as component A, composed of        -   aa) at least one amino-containing polymer as component Aa;        -   ab) at least one aromatic compound as component Ab, being a            phenol or quinone or containing a phenolic or quinonoid            structural unit;        -   ac) if desired, an aldehyde as component Ac;    -   b) water or another solvent suitable for dissolving, dispersing,        suspending or emulsifying the polymer (component A), as        component B;    -   c) if desired, surface-active compounds, dispersants, suspension        media and/or emulsifiers as component C.

Preference is given to compositions which are suitable for nickeling andcoppering plastics surfaces; for example, for coppering in themanufacture of printed circuit boards. The plastics surfaces areprepared for the metallizing operation using common industrialprocesses. The compositions of the invention serve for metallizing theplastic, but may also be employed, where appropriate, in the context ofthe pretreatment for the metallizing operation.

For the purposes of the present specification, the term “composition” isused to refer both to the ready-to-use compositions and to concentrates.The concentrations specified hereinbelow for the individual componentsrefer to the ready-to-use compositions. The skilled worker isnevertheless aware that, in concentrates, the concentrations of theindividual components are, correspondingly, higher.

Component A

Component A is a polymer composed of at least one amino-containingpolymer as component Aa and at least one aromatic compound as componentAb which is a phenol or quinone or comprises a phenolic or quinonoidstructural unit. If desired, the polymer comprises as component Ac abuilding block originating from a reaction with an aldehyde.

The term “polymers” should be understood in general to refer tocompounds which contain at least three repeating units, preferably morethan 10 repeating units. The weight average of the molecular weight ofthe inventively used polymers is in general from 500 to 5 000 000 g/mol,preferably from 1000 to 1 500 000 g/mol. The polymer may also be incrosslinked form, with the consequence that no molecular weight can bespecified although the polymer can be dispersed, emulsified or suspendedin common industrial solvents.

Component Aa

Component Aa is an amino-containing polymer. Polymers used withpreference include polyethyleneimine, polyvinylamine,poly(vinylformamide-co-vinylamine), polylysine, and polyaminostyrene.Also suitable are polyamine derivatives which still contain aminogroups, examples being the reaction products of polyamines withcarboxylic acids and/or sulfonic acids, or carboxymethylation productsof polyamines. Further suitable and particularly preferred polymers areamino-containing derivatives of polycarboxylates, especially thereaction products of diamines and copolymers containing repeating.maleic, acrylic or methacrylic acid units, such as the reaction productsof styrene-maleic anhydride copolymers with diamines. Very particularpreference is given to polymers of the formulae (I) and (II):

In these formulae, R is an organic radical, preferably an alkylene,cycloalkylene, arylene, arylalkylene or alkylarylene radical. Thisradical may be interrupted by heteroatorns or substituted as desired,suitable substituents being alkyl, alkenyl, aryl, alkylaryl or arylalkylradicals, which may in turn be interrupted by heteroatoms or substitutedby groups containing heteroatoms. Preferably, R is a C₂₋₃₂-alkyleneradical; with particular preference, it is a C₂₋₁₄-alkylene radicalwhich may be interrupted by heteroatoms selected from —N— and —O— andmay carry C₁₋₆-alkyl radicals or groups containing heteroatoms, examplesbeing amino groups. Particularly preferred radicals are ethyl, n-butyl,and n-hexyl radicals.

R′, R″ and R′″ independently of one another denote hydrogen or anydesired organic radicals. Suitable organic radicals are generally alkyl,cycloalkyl, alkenyl, aryl, alkylaryl, and arylalkyl radicals which may,where appropriate, be interrupted by heteroatoms and/or substituted bygroups containing heteroatoms. Preferably, R′, R″ and R′″ independentlyof one another denote hydrogen or hydrocarbon, with particularpreference hydrogen, C₁₋₆ alkyl, C₆₋₁₀ aryl, with very particularpreference methyl, ethyl, isopropyl, n-propyl or phenyl.

The amino-containing polymers are available commercially(polyethyleneimine, polyvinyl-amine) or may be prepared by methods whichare known to the skilled worker. Suitable processes for preparingpolyvinylamine are disclosed, for example, in EP-A 216 387, DE-A 38 42820, DE-A 195 266 26, DE-A 195 159 43. The polymers of the formulae (I)and (II) used with particular preference are preparable, for example, inaccordance with the process disclosed in U.S. Pat. No. 4,046,748.

It is also possible to use the polymer in a mixture with low molecularweight amines. Suitable low molecular weight amines in this case areselected from the group consisting of ethylenediamine,H₂N(—C₂H₄—NH)_(n)—H where n=2-4, and H₂N(—CH₂)_(n)—H where n=1-18,preferably n=2, 3, 4, 6, 8, 10 or 12.

The amino-containing polymers are generally in desalted form. In thecase of copolymers containing repeating vinylamine and vinylformamideunits, the degree of hydrolysis is generally from 0.5 to 100%,preferably from 50 to 100%.

Component Ab

Component Ab is a phenol or quinone or a compound which comprises aphenolic or quinonoid structural unit.

Suitable quinones or quinone derivatives are generally systems derivedfrom o-benzoquinone or from p-benzoquinone. Preference is given to usingsystems derived from p-benzoquinone. Particularly preferred compoundsare those of the formula (III):

in which R¹, R², R³ and R⁴ independently of one another may be hydrogenor alkyl, alkenyl, cycloalkyl, aryl, alkylaryl or arylalkyl radicals.Preferably, R¹ to R⁴ independently of one another are hydrogen or C₁ toC₁₄ alkyl radicals, C₂ to C₁₄ alkenyl radicals, C₆ to C₁₄ aryl radicalsor C₅ to C₁₆ cycloalkyl radicals. It is also possible for R¹ and R²and/or R³ and R⁴ in pairs to form a cyclic radical which may besaturated or unsaturated. This cyclic radical is preferably a ringcomposed of a total of six carbon atoms, with two carbon atomsoriginating from the parent structure in formula (III). The radicalsmentioned may in turn be substituted by alkyl, alkenyl, cycloalkyl,aryl, arylalkyl or alkylaryl radicals and/or interrupted by heteroatomsor substituted by groups containing heteroatoms. With particularpreference, the radicals R¹ to R⁴ in formula (III) independently of oneanother denote hydrogen and methyl. Compounds of the formula (III) usedwith particular preference are selected from the group consisting ofbenzoquinone, 2,3,5-trimethyl-benzoquinone, 2,6-dimethylbenzoquinone,naphthoquinone, and anthraquinone.

Suitable phenols or compounds which comprise a phenolic or quinonoidstructural unit are compounds of the formula (IV):

In this formula, the radicals R⁵, R⁶, R⁷, R⁸ and R⁹ independently of oneanother have the definition specified for R¹ to R⁴. Additionally, theradicals R⁵ and R⁶, R⁶ and R⁷, R⁷ and R⁸, and/or R⁸ and R⁹ may in pairsform a cyclic radical as defined for R¹ and R² and, respectively, R³ andR⁴. Furthermore, one or two of the radicals R⁵ to R⁹ may denote —O⁻M⁺.

M⁺ in formula (IV) denotes hydrogen or a -cation. In general, M⁺ is analkali metal cation, preferably a sodium or potassium ion. It is,however, also possible for M⁺ to be a cation with a valence of two ormore, preferably an alkaline earth metal cation or Zn, Mn or Cr(III),with particular preference magnesium or calcium.

In addition to the abovementioned radicals, R⁵ to R⁹ may also denote—SO₃ ⁻M⁺, —NO₂, halogen, —COO⁻M⁺, —C(O)R″″ (where R″″ is hydrogen or analkyl, aryl, cycloalkyl, aralkyl or alkaryl radical), —N(R″″)₂, —OR″″ or—SH or other functional groups which are known to the skilled worker. Ingeneral, only one of the radicals R⁵ to R⁹ has one of the last-mentioneddefinitions.

Preferred compounds of the formula (IV) are 1-, 2- or 3-valent phenolswhich may be substituted by the radicals mentioned above. In thiscontext, not only the phenolic compounds mentioned but also their saltsare suitable.

Particularly preferred compounds of the formula (IV) are phenol,4,4′-dihydroxydiphenyl sulfide, dihydroxydiphenyl sulfoxide,phenolsulfonic acid, 1,4-dihydroxynaphthalene, nitrophenol,(N,N-dimethylamino)-1-phenol, hydroxythioanisole, pyrogallol,phloro-glucinol, 1,2,4-trihydroxybenzene,2,2′,4,4′-tetrahydroxybenzophenone, salicylic acid, 2,3-dihydroxybenzoicacid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid,trihydroxybenzoic acids such as gallic acid, for example, alkylsalicylates such as ethyl salicylate, for example, alkyl3,4-dihydroxybenzoates such as ethyl 3,4-dihydroxy-benzoates, forexample, alkyl gallates such as propyl gallate, for example,2,3-dihydroxy-benzaldehyde, 2,4-dihydroxybenzaldehyde,2,5-dihydroxybenzaldehyde, 2,3,4-trihydroxy-benzaldehyde,((4-tert-butyl-2,6-dimethyl-3-hydroxy)benzyl)imidazoline,(s)-2-(3,4-dihydroxybenzyl)-2-hydrazinopropionic acid,1,2-dihydroxy-4-tert-butylbenzene, 2-(4-hydroxyphenoxy)propionic acid,2-(4-hydroxyphenyl)ethylamine, 2-(4-hydroxy-phenyl)ethylamine,2,3,5-trimethylbenzene-1,4-diol,2,3-dihydro-1,4-dihydroxyanthra-quinone, 2,4-dichlorophenol,2,5-dihydroxytoluene, 2,5-dimethylphenol,2,5-di-tert-pentyl-hydroquinone, 2,7-dihydroxynaphthalene,2-allylphenol, 2-amino-4,6-dinitrophenol, 2-hydroxy-3-methylbenzoicacid, 2-hydroxyacetophenone, 2-hydroxyanthraquinone,2-hydroxybenzaldehyde, methyl 2-hydroxybenzoate, 2-hydroxyphenylaceticacid, 2-hydroxyphenyl methylcarbamate, 2-naphthol-3,6-disulfonic acid,2-tert-butyl-4-methyl-phenol, 2-tert-butylhydroquinone,3,5-di-tert-butyl-4-hydroxytoluene, 3-aminophenol,3-carboxy-2-hydroxynaphthalene, 3-methylphenol,3-tert-butyl-4-hydroxyanisole,4-(2-(3-(4-hydroxyphenyl)-1-methylpropyl)amino)ethyl)-1,2-dihydroxybenzene,4,4′-dihydroxy-biphenyl, 4-acetylamino-1-hydroxybenzene, 4-chlorophenol,4-diazo-3-hydroxy-naphthalene-1-sulfonic acid, 4-hydroxyacetophenone,4-hydroxybenzoic acid, propyl 4-hydroxybenzoate, 4-hydroxybenzophenone,4-hydroxymandelic acid, 4-methoxyphenol, 4-methylphenol,4-nitro-2-aminophenol-6-sulfonic acid, 5-chloro-2-hydroxytoluene,5-nitro-2-aminophenol, 6-acetylamino-2-amino-1-hydroxybenzene-4-sulfonicacid, 6-hydroxynaphthalene-2-sulfonic acid, 8-hydroxy-2-methylquinoline,8-hydroxyquinoline, adrenaline, alpha-tocopherol, amylmetacresol,bis(4-hydroxyphenyl) sulfone, bisphenol A, pyrocatechol, dopamine,estradiol, hydroquinone, isatinbiscresol,N,N-bis(hydroxyethyl)-4-hydroxyaniline, N,N-diethyl-m-aminophenol,N,N-dimethyl-2-(4-hydroxyphenyl)-ethylamine sulfate,N,N-dimethyl-4-hydroxyphenylethylamine,N,N′-disalicylalethylene-diamine, octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, octylphenol,p-dodecylphenol, and p-isononylphenol. In addition to the phenoliccompounds mentioned above, their salts are also suitable.

Particular preference is given to using phenol and pyrocatechol.

Component Ac

The polymer (component A) is composed, if desired, of an aldehyde asfurther component, component Ac. This further component is present, forexample, when the polymer is prepared by Mannich reaction. In general,suitable aldehyde components Ac include all aldehydes. It is preferredto use aldehydes of the formula (V).

In this formula, R¹⁰ denotes hydrogen, alkyl, alkenyl, cycloalkyl, aryl,aralkyl or alkaryl. It is possible here for the radical R¹⁰ to besubstituted by heteroatoms and/or groups which carry heteroatoms. It isalso possible for the radicals mentioned for R¹⁰ to be interrupted byheteroatoms. R¹⁰ is preferably hydrogen, C₁₋₁₄ alkyl, C₁₋₁₄ alkenyl,C₅₋₁₆ cycloalkyl, C₆₋₁₄ aryl, C₇₋₁₄ aralkyl or C₇₋₁₈ alkaryl. Theseradicals may be substituted by radicals containing heteroatoms andselected from the group consisting of halogen, preferably chlorine orbromine, NO₂, SH, OH, acetyl, carboxyl, and —C(O)-phenyl, or interruptedby heteroatoms. The radical R¹⁰ may in turn be substituted itself byalkyl, cycloalkyl, aryl, alkaryl or aralkyl radicals, which in turn maycarry groups containing heteroatoms, and/or whose chain and/or ring maybe interrupted by heteroatoms.

A particularly preferred component Ac comprises at least one componentselected from the group consisting of formaldehyde, ethanal, propanal,butanal, citronellal, benzaldehyde, 2-chlorobenzaldehyde,2-hydroxybenzaldehyde, 2-propenal, 3,3-dimethylacrolein,4-methylbenzaldehyde, 4-(1,1-dimethylethyl)benzaldehyde, anisaldehyde,4-chloro-benzaldehyde, 3-hydroxy-2,2-dimethylpropanal,7-hydroxy-3,7-dimethyloctanal, N-hexanal, 2-furfural, methyl3-methyl-4-oxo-2-butenoate, 3-methylbutanal, 2-ethyl-hexanal,2-methylpropanal, 2-phenylpropionaldehyde,3,7-dimethylocta-2,6-dien-1-al,4-(1,1-dimethylethyl)-alpha-methylbenzopropanal, pentanal,2-methylpentanal, 2-methyl-2-pentenal, 3-acetyloxy-2-methylpropanal,4-acetoxy-2-methyl-2-butenal, 3-formylpinane, 4-benzyloxybenzaldehyde,2-methyl-4,4-diacetoxy-2-butenal, 2-methyl-2-propenal,terephthalaldehyde, 3-(4-methylphenyl)-2-methyl-2-propenal,4-formylbenzoic acid, 3-nitrobenzaldehyde,3-formyl-4-methyltetrahydropyran, 2-methyl-3-methylthiopropanal, methyl2-formyl-2-methylpropionate, o-phthalaldehyde, retinal,3-(4-methoxyphenyl)-2-methyl-2-propenal, 2,3-diphenylpropenaln methyl3-formyl-2-methylpropionate, and cinnamaldehyde.

The polymers (component A) may be prepared by methods which are known tothe skilled worker. Preferred polymers are those obtained by Michaelreaction (R1) and those obtained when a suitable aldehyde (component Ac)is added on in a Mannich reaction (P2). The scheme below shows a Michaelreaction (R1) involving—as an example—benzoquinone:

In this scheme, R¹¹ denotes hydrogen or an organic radical, depending onthe amino-containing polymer (component Aa) used. Preferably, R¹¹ ishydrogen or methyl.

The Mannich reaction (R2) likewise used with preference for preparingthe polymers (component A) is depicted below with the involvement—as anexample—of phenol:

The definitions of R¹⁰ and R¹¹ have already been given above.

In the compositions of the invention, component A is used generally inan amount of from 0.01 to 400 g/l, preferably from 0.2 to 100 g/l, withparticular preference from 1 to 50 g/l, based in each case on one literof the composition. The precise amount of component A is dependent onthe respective process for the treatment of metal surfaces and also onthe metal surface in question.

Component B

Component B is water or another solvent suitable for dissolving ordispersing, suspending or emulsifying the polymer (component A).Suitable other solvents besides water are, for example, aliphatic oraromatic solvents such as benzene, toluene, and xylene, halogenatedsolvents such as methylene chloride and chloroform, alcohols such asmethanol and ethanol, ethers, such as diethyl ether and tetrahydrofuran,polyethers, especially polyethylene glycol, ketones, such as acetone,and mixtures of these solvents with one another and/or with water. It isparticularly preferred to use exclusively water as solvent.

The pH is determined by the nature of the application. By way ofexample, pickling and phosphating baths are generally highly acidic, andelectroplating baths basic or acidic depending on the nature of thebath. pH values suitable for the specific applications are known to theskilled worker.

The amount of water or another solvent is a function of whether thecomposition of the invention is a ready-to-use composition or aconcentrate, and also of the respective end use. Basically, the amountis a function of the concentrations of the individual components thatare indicated for the ready-to-use composition.

Component C

Where appropriate, the composition of the invention may further comprisesurface-active compounds, emulsifiers and/or dispersants. Suitablesurface-active compounds are surfactants, which may be cationic,anionic, zwitterionic or nonionic. Examples of suitable surfactants arealkyl and alkenyl alkoxylates of the type R-EO_(n)/PO_(m) in which R aregenerally linear or branched C₆-C₃₀ alkyl radicals, preferably C₈-C₂₀alkyl radicals, and EO is an ethylene oxide unit and PO is a propyleneoxide unit, the sequential arrangement of EO and PO being arbitrary, andn and m independently of one another being >1 and <100, preferably >3and <50, examples being Emulan®, Lutensol® and Plurafac® (from BASF),alkylphenol ethoxylates, EO/PO block copolymers (Pluronic®, from BASF),alkyl ether sulfates, and alkylammonium salts, referred to as quats.

The amount of these components in the composition of the invention isgenerally 0.01-100 g/l, preferably from 0.1 to 20 g/l.

In one preferred embodiment, the composition of the invention is usedfor the treatment of metal surfaces and comprises further to componentsA, B and, where appropriate, C:

-   -   d) at least one salt, acid or base based on transition metal        cations, transition metal oxo anions, fluorometallates or        lanthanoids as component D, and/or    -   e) at least one acid selected from the group consisting of        phosphoric acid, sulfuric acid, sulfonic acids, nitric acid,        hydrofluoric acid, and hydrochloric acid, as component E, and/or    -   f) at least one further corrosion inhibitor as component F,        and/or    -   g) compounds of Ce, Ni, Co, V, Fe, Zn, Zr, Ca, Mn, Mo, W, Cr        and/or Bi as component G, and/or    -   h) further auxiliaries and additives as component H.

These compositions are especially suitable for picking or passivating,especially phosphating, or as rust converters for the metal surfacesmentioned in the present specification.

Component D

Suitable components D are salts, acids, and bases based on transitionmetal cations, transition metal oxo anions, fluorometallates orlanthanoids. Suitable transition metal cations are, in particular,fluorometallates of Ti(IV), Zr(IV), Hf(IV) and/or Si(IV), and aparticularly suitable lanthanoid is Ce. Also suitable are tungstates andmolybdates.

Compositions in accordance with the present specification which comprisecomponent D are especially suitable either for depositing a corrosionprotection coat on a metal surface or for reinforcing the corrosionprotection effect of a corrosion coat already deposited on the metalsurface. In the compositions of the invention, the inventively usedpolymers (component A) have an outstanding corrosion protection effect.

The amount of component D—where component D is present in thecompositions of the invention—is preferably from 0.02 to 20 g/l.

Component E

In addition to or instead of component D, the compositions of theinvention may further comprise at least one acid selected from the groupconsisting of phosphoric acid, sulfuric acid, sulfonic acids such asmethanesulfonic acid, vinylsulfonic acid, allylsulfonic acid,m-nitrobenzenesulfonic acid, naphthalenesulfonic acid, and derivativesthereof, nitric acid, hydrofluoric acid, and hydrochloric acid. Thenature of the acid used is dependent on the type of treatment of themetal surface. Accordingly, phosphoric acid is generally used inphosphating baths for phosphating steel surfaces. In this case thecomposition of the invention is a phosphating solution. A distinction ismade here between what are known as “non-film-forming” phosphatingsolutions, i.e., solutions containing no divalent metals. Thesenon-film-forming phosphating solutions are in the form, for example, ofan iron phosphating solution. Where the phosphating solutions do containions of divalent metals, e.g. zinc and/or manganese, the phosphatingsolutions are said to be film-forming. Compositions in accordance withthe present specification that comprise nitric acid are particularlysuitable for the surface treatment of zinc and its alloys, whereascompositions comprising hydrofluoric acid are particularly suitable forthe surface treatment of aluminum and its alloys.

The amount of acid used may vary depending on the field of application.In general, where component E is present in the compositions of theinvention, it is used at from 0.2 to 200 g/l, preferably from 2 to 100g/l.

Component F

In addition to or instead of components D and/or E, the compositions ofthe invention may comprise at least one further corrosion inhibitor.Suitable corrosion inhibitors are selected from the group consisting ofbutynediol, benzotriazole, aldehydes, amine carboxylates, aminophenolsand nitrophenols, amino alcohols, aminobenzimidazole, aminoimidazolines,aminotriazole, benzimidazolamines, benzothiazoles, benzotriazolederivatives, esters of boric acid with various alkanolamines, such asboric acid diethanolamine ester, for example, carboxylic acids and theiresters, quinoline derivatives, dibenzyl sulfoxide, dicarboxylic acidsand their esters, diisobutenylsuccinic acid, dithiophosphonic acid,fatty amines and fatty acid amides, guanidine derivatives, urea and itsderivatives, laurylpyridinium chloride, maleamides,mercaptobenzimidazole, N-2-ethylhexyl-3-amino-sulfopropionic acid,phosphonium salts, phthalamides, amine- and sodium-neutralizedphosphoric esters of alkyl alcohols, and also these phosphoric estersthemselves, phosphoric esters of polyalkoxylates, and particularly ofpolyethylene glycol, polyetheramines, sulfonium salts, sulfonic acidssuch as methanesulfonic acid, for example, thioethers, thioureas,thiuramide sulfides, cinnamic acid and its derivatives, zinc phosphatesand zinc silicates, and zirconium phosphates and zirconium silicates.

As further corrosion inhibitors it is preferred to use butynediol andbenzotriazole (especially for the surface treatment of copper).

If used at all in the compositions, the corrosion inhibitors are used inan amount of generally from 0.01 to 50 g/l, preferably from 0.1 to 20g/l, with particular preference from 1 to 10 g/l.

Component G

In addition to or, where appropriate, instead of the abovementionedcomponents, it is also possible to employ compounds of Ce, Ni, Co, V,Fe, Zn, Zr, Ca, Mn, Mo, W, Cr and/or Bi. In general, the use ofcomponent A in accordance with the invention in the compositions resultsin such good corrosion protection properties that the addition of theabovementioned compounds is unnecessary. Preferably, the compositions ofthe invention are free from Cr(VI). Where, nevertheless, theaforementioned compounds (component G) are used, it is preferred to usecompounds selected from Fe, Zn, Zr and Ca. The amount of these compoundsin the compositions of the invention, where they are present at all, isgenerally from 0.01 to 100 g/l, preferably from 0.1 to 50 g/, withparticular preference from 1 to 20 g/l.

Component H

In addition to one or more of the above components D to G, thecompositions of the invention may comprise further auxiliaries andadditives. Suitable auxiliaries and additives include conductivitypigments or conductive fillers, e.g., iron phosphide, vanadium carbide,titanium nitride, carbon black, graphite, molybdenum disulfide or tin-or antimony-doped barium sulfate, with iron phosphide being preferred.Conductivity pigments or conductive fillers are added -to thecompositions of the invention in order to improve the weldability of themetal surfaces to be treated or in order to improve subsequent coatingwith electrocoat materials. Moreover, silica suspensions may beemployed, particularly when the compositions are used for the treatmentof surfaces comprising aluminum.

These auxiliaries and/or additives are generally present in a finelydivided form; in other words, their mean particle diameters aregenerally from 0.005 to 5 μm, preferably from 0.05 to 2.5 μm. The amountof the auxiliaries and additives is generally from 0.1 to 50% by weight,preferably from 2 to 35% by weight, based on the overall mass of thecompositions of the invention.

The compositions of the invention may further comprise additions forimproving the forming characteristics, examples being wax-basedderivatives based on natural or synthetic waxes, e.g., waxes based onacrylic acid, polyethylene waxes, polytetrafluoro-ethylene (PTFE) waxesor wax derivatives or paraffins and their oxidation products.

Depending on their area of application, the compositions of theinvention may comprise polymer dispersions based on styrene,4-hydroxystyrene, butadiene, acrylic acid, acrylic esters, acrylamides,acrylates, methacrylic acid, methacrylic esters, methacrylamides,methacrylates, and derivatives of acrylamide. It is also possible forthe compositions of the invention to comprise polyurethane dispersionsand polyesterurethane dispersions or polyurea dispersions.

Another group of compounds that may be present in the compositions ofthe invention embraces polyethylene glycols, polypropylene glycols,copolymers of ethylene oxide, and copolymers of propylene oxide.

Where the compositions of the invention are used in powder coatingmaterials, they may further comprise epoxy resins and/or condensationresins of formaldehyde with phenol, urea, melamine, phenolsulfonic acidor naphthalenesulfonic acid.

When the compositions of the invention are employed in rust converters,they may further comprise polyvinylbutyral.

Depending on the precise makeup of the compositions of the inventioncomprising component A, they may be used in all applications for thetreatment of metal surfaces, particularly in those applications wherethe corrosion of metal surfaces may pose a problem. Examples of suchapplications are paint stripping, metal pickling, electro-polishing,chemical deburring, chemical and electrochemical metal deposition(particularly of Cu, Ni, Pd, Zn, Co, Mn, Fe, Mg, Sn, Pb, Bi, Ag, Au, andtheir alloys), conversion coating (especially no-rinse conversioncoating, i.e., processes with a reduced number of rinsing operations, onzincked steel and aluminum, for example), corrosion protection(especially on copper, in printed circuit board manufacture forinstance, and on steel) and lubricating and greasing (especially inconnection with cold forming). The manner of application is inaccordance with common industry methods, with the additionalobservations that the compositions of the invention are used in unisonwith further components common in industry for the application inquestion or that they are brought into contact with the metal inadditional treatment steps, such as spraying, dipping, surface coatingor electrocoating, for example, using appropriate formulations of thecorrosion inhibitor compositions of the invention such as solutions,emulsions, dispersions, suspensions or aerosols.

The present specification further provides compositions for metaldeposition, comprising—in addition to components A, B, and, whereappropriate, C—

-   -   i) at least one metal oxide and/or metal salt as component I,    -   j) where appropriate, at least one complexing agent as component        J,    -   k) where appropriate, at least one acid or an alkali metal salt        or alkaline earth metal salt of the corresponding acid, as        component K, and    -   l) where appropriate, further additions as component L.

These compositions of the invention are particularly suitable for thedeposition of metals or metal alloys on metal or plastics surfaces.Suitable metal surfaces have already been specified above. Thedeposition of metals or metal alloys on plastics surfaces takes placepreferably in the context of the manufacture of printed circuit boards.Deposition is preferably carried out in a chemical or electrochemicalprocess.

Component I

Suitable metal oxides or metal salts are the oxides or salts of metalsselected from the group consisting of Zn, Ni, Cu, Au, Pd, Sn, Co, Mn,Fe, Mg, Pb, Bi and Ag. The metals may be deposited in the form of themetal used or—when using different metals—in the form of alloys of saidmetals with one another or with other metals. Preferred alloys are CuZn,CuSn, CuNi, SnPb, SnAgBiCu, SnAgCu, SnBi, SnAg, SnCu, NiPd, NiP, ZnFe,ZnNi, ZnCo, and ZnMn. The aforementioned ingredients of the alloys maybe present in any desired concentrations in the alloy. Particularpreference is given to depositing Zn, Cu, and Ni, and also alloys ofthese metals with other metals or with one another. In the context ofthe deposition of metals or metal alloys on plastics surfaces, Ni and Cuare particularly preferred. Besides their use as metal oxides, themetals may be used as metal salts selected from the correspondingsulfates, salts with sulfonic acids, chlorides, carbonates, sulfamates,fluoroborates, cyanides, and acetates.

The concentration of the metal ions in the compositions of the inventionis generally from 0.01 to 100 g/l, preferably from 0.1 to 50 g/l, withparticular preference from 2 to 20 g/l, based on the amount of the metalused.

Component J

The compositions of the invention may, where appropriate, furthercomprise a complexing agent. Examples of suitable complexing agentsinclude ethylenediaminetetraacetic acid (EDTA), ethylenediamine (ED),citric acid, and salts of said compounds.

Component K

The compositions of the invention may, where appropriate, furthercomprise at least one acid or an alkali metal salt or alkaline earthmetal salt of the corresponding acid, selected preferably from the groupconsisting of HNO₃, H₂SO₄, H₃PO₄, formic acid, and acetic acid. The acidis generally used in an amount of from 0.5 to 700 g/l, preferably from 5to 200 g/l.

Component L

In addition to the abovementioned components, the compositions of theinvention may include further additions, which may differ depending onintended applications, metal to be deposited, objective, and processemployed. Suitable additions are1-(2-vinylpyridinium)-2-ethylsulfobetaine,1,1-dimethyl-2-propynyl-1-amine, 1-pyridinium-2-ethylsulfobetaine,1-pyridinium-2-hydroxy-3-propylsulfobetaine,1-pyridinium-3-propylsulfobetaine, 2,2′-di-chlorodiethyl ether,2,5-dimethyl-3-hexyne-2,5-diol, 2-butyne-1,4-diol, 2-butyne-1,4-diolethoxylate, 2-butyne-1,4-diol propoxylate, sodium3-(2-benzothiazolylthio)-1-propane-sulfonate, sodium,3,3′-dithiobis(1-propanesulfonate),3-[(aminoiminomethyl)thio]-1-propanesulfonic acid, sodium3-[(dimethylamino)thioxomethyl]thio-1-propanesulfonate, potassium3-[ethoxythioxomethyl]thio-1-propanesulfonate, sodium3-chloro-2-hydroxy-1-propanesulfonate, 3-hexyne-2,5-diol, sodium3-mercapto-1-propanesulfonate, 4,4-di-hydroxydiphenyl sulfone,4-methoxybenzaldehyde, aldehydes, alkylphenyl polyethylene oxidesulfopropyl ether potassium salts, alkyl polyethylene oxide sulfopropylether potassium salts such as, for example, tridecyl/pentadecylpolyethylene oxide sulfopropyl ether potassium salt, sodiumallylsulfonate, amidosulfonic acid, amine- and sodium-neutralizedphosphoric esters of alkyl alcohols, amine carboxylates, aminophenolsand nitrophenols, amino alcohols, aminobenzimidazole, aminoimidazolines,aminotriazole, methyl benzylacetoacetate, benzylacetone,benzimidazolamines, benzothiazoles, benzotriazole and its derivatives,benzyl pyridine-3-carboxylate, bisphenol A, esters of boric acid withvarious alkanolamines such as, for example, boric acid diethanol ester,carboxylic acids and their esters, carboxyethylisothiuronium betaine,quinoline derivatives, copolymers of ethylene and acrylic acid,copolymers of imidazole and epichlorohydrin, copolymers of imidazole,morpholine, and epichlorohydrin, copolymers ofN,N′-bis[3-(dimethylamino)propyl]urea and 1,1′-oxybis[2-chloroethane],copolymers of n-butyl acrylate, acrylic acid, and styrene, dibenzylsulfoxide, dicarboxylic acids and their esters,diethylenetriaminepentaacetic acid and salts derived from it,diisobutenylsuccinic acid, disodium ethylenebisdithiocarbamate,dithiophosphonic acid, ethylamidosulfonic acid,ethylenediaminetetraacetic acid and salts derived from it,ethylglycinediacetic acid and salts derived from it, ethylhexanolethoxylate, fatty amines and fatty acid amides, formaldehyde, glycerolethoxylate, guanidine derivatives, urea and its derivatives,hydroxyethyliminodiacetic acid and salts derived from it, imidazole,isopropylamidosulfonic acid, isopropylamidosulfonyl chloride,lauryl/myristyltrimethyl-ammonium methosulfate, laurylpyridiniumchloride, maleamides, mercaptobenzimidazole, methylamidosulfonic acid,N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine,N,N-diethyl-2-propyn-1-amine, N,N-diethyl-4-amino-2-butyn-1-ol,N,N-dimethyl-2-propyn-1-amine, N-2-ethylhexyl-3-aminosulfopropionicacid, N-allylpyridinium chloride, sodium salt of sulfated alkylphenolethoxylates, sodium 2-ethylhexyl sulfate, nicotinic acid,nitrilotriacetic acid and salts derived from it, sodiumnitrobenzenesulfonate, N-methallylpyridinium chloride,ortho-chlorobenzaldehyde, phosphonium salts, phthal-amides, picolinicacid, polyetheramines, polyethyleneimines, polyvinylimidazole, propargylalcohol, propargyl alcohol ethoxylate, propargyl alcohol propoxylate,sodium propynesulfonate, propiolic acid, propylenediaminetetraaceticacid and salts derived from it, pyrrole, quaternized polyvinylimidazole,reaction product of 2-butyne-1,4-diol and epichlorohydrin, reactionproduct of 2-butyne-1,4-diol and propane sultone, reaction product ofsaccharin and propane sultone, reaction product of alkylethoxylate/propoxylate with propane sultone, reaction product ofpolyethyleneimine with propane sultone, reaction product of β-naphtholethoxylate/propoxylate with propane sultone, resorcinol ethoxylate,saccharin, β-naphthol ethoxylate, sodium β-naphthol ethoxylate sulfate,sulfonium salts, sulfonic acids such as methanesulfonic acid, forexample, thiodiglycol, thiodiglycol ethoxylate, thioethers, thioureas,thiuramide sulfides, sodium vinylsulfonate, cinnamic acid and itsderivatives, zinc phosphates and zinc silicates, zirconium phosphatesand zirconium silicates, hypophosphites (e.g., sodium hypophosphite),NaBH₄, dimethylaminoborane, diethylaminoborane, hydrazine, formaldehyde,urotropin, palladium chloride, sodium stannate, HF_(x)BF₃, polyethyleneglycols of molecular weight 100-1 000 000 g/mol, block copolymers ofethylene oxide and propylene oxide, examples being Pluronic grades fromBASF Aktiengesellschaft, Ludwigshafen/Rhein, and random copolymers ofethylene oxide and propylene oxide, especially those with molecularweights in the range 100-2000 g/mol.

Using the compositions of the invention in accordance with thisembodiment, it is possible in particular to obtain metal depositions byelectrochemical or chemical means. Whether chemical or electrochemicaldeposition is performed depends on the metal, on the metal surface, andon the desired result.

Process for the Treatment of a Metal or Plastics Surface

The present specification further provides a process for the treatmentof a metal surface, which involves contacting the metal surface with apolymer (component A) composed of:

-   -   aa) at least one amino-containing polymer as component Aa,    -   ab) at least one aromatic compound as component Ab, being a        phenol or quinone or containing a phenolic or quinonoid        structural unit, and    -   ac) if desired, an aldehyde as component Ac.

This polymer and also preferred embodiments of the polymer and suitablepreparation processes have already been mentioned above (see componentA). Suitable metal surfaces and also preferred embodiments of the metalsurfaces have likewise been mentioned above.

Suitable processes include, for example, paint stripping, metalpickling, electropolishing, chemical deburring, chemical andelectrochemical metal deposition, conversion coating (especiallyno-rinse conversion coating), corrosion protection (especially oncopper, such as in circuit board manufacture, and on steel),lubricating, and greasing (especially in the case of cold forming).

In the process of the invention, the polymer may be present as asolution, emulsion, suspension or aerosol. With preference, the polymer(component A) is present in one of the abovementioned compositions ofthe invention.

The nature of application corresponds to common industry methods, withthe added note that the polymers (component A) used in accordance withthe invention are employed together with further components customary inindustry for the corresponding application, or that they are contactedwith the metal in additional treatment steps, such as spraying, dipping,surface coating or electrocoating, for example, using suitableformulations of the polymers.

In one preferred embodiment of the process of the invention, a metalsurface is contacted with a composition comprising components A, B and,where appropriate, C, or with a composition comprising not onlycomponents A, B and, where appropriate, C but also, as furthercomponents, components D and/or E and/or F and/or G and/or H. Suitablecomponents B to H have been set out above. In this preferred embodimentof the process of the invention, it is preferred to carry out picklingor passivating, especially phosphating, of the metal surface. Suitableprocess steps and apparatus for passivating, especially phosphating, orfor pickling metal surfaces are known to the skilled worker.

In general, the metal surface treatment, in particular a passivation,with particular preference a phosphating or pickling treatment, iscarried out by spraying a composition of the invention onto the metalsurface or by immersing the metal surface in a composition of theinvention, depending on the number, size and shape of the parts to betreated.

Where phosphating of metal strips is carried out, the compositions ofthe invention comprising phosphoric acid as component E may be appliedby a roll-on or dry-in-place or no-rinse process, with the phosphatingcomposition of the invention being applied to the metal strip and driedwithout rinsing, a polymer film being formed.

The present specification further provides a process comprising thefollowing steps:

-   -   a) where appropriate, cleaning the metal surface to remove oils,        fats, and dirt,    -   b) where appropriate, washing with water,    -   c) where appropriate, pickling to remove rust or other oxides,        in the presence or absence of the polymer (component A) used in        accordance with the invention,    -   d) where appropriate, washing with water,    -   e) treatment of the metal surface in the presence of the polymer        (component A) used in accordance with the invention,    -   f) where appropriate, washing with water,    -   g) where appropriate, aftertreatment, in the presence or absence        of the polymer (component A) used in accordance with the        invention.

The treatment of the metal surface in step e) may be a passivatingtreatment, in particular phosphating, in accordance with processes knownto the skilled worker. A protective coat, film or impregnation isapplied to the metal. Where phosphating is carried out in step e), it ispossible to aftertreat the metal surface in step g) with passivatingadditives.

Washing with water takes place between the individual process steps inorder to prevent contamination of the solution required for thefollowing step with components of the solution used in the precedingstep. It is, however, also possible to carry out the process of theinvention as a no-rinse process, i.e., without steps b), d), and f).

The steps of cleaning (step a)) and of treating the metal surface in thepresence of the polymer (component A) used in accordance with theinvention, preferably of passivating (step e)), may also be performed inone step, i.e., with a formulation comprising not only the customarycleaning agents but also the composition of the invention.

Following process steps a) to g), the metal surface may be provided witha surface coating material. Surface coating takes place likewise inaccordance with processes known to the skilled worker.

A further preferred embodiment of the present specification concerns aprocess for the deposition of metals or metal alloys on a metal surface,the metal surface being contacted with a composition comprisingcomponents A, B and, where appropriate, C, or with a compositioncomprising not only components A, B, and, where appropriate, C but also,as further components, components I, J where appropriate, K whereappropriate, and L where appropriate. Suitable components A, B, C, I, J,K, and L have already been mentioned above.

A further embodiment of the present specification concerns a process forthe deposition of metals or metal alloys on a plastics surface, theplastics surface being contacted with a polymer (component A) composedof

-   -   aa) at least one amino-containing polymer as component Aa,    -   ab) at least one aromatic compound as component Ab, being a        phenol or quinone or containing a phenolic or quinonoid        structural unit, and    -   ac) if desired, an aldehyde as component Ac.

With preference, in the process of the invention, the plastics surfaceis contacted with a composition comprising components A, B and, whereappropriate, C, or with a composition comprising not only components A,B, and, where appropriate, C but also, as further components, componentsI, J where appropriate, K where appropriate, and L where appropriate.Suitable components A, B, C, I, J, K, and L have already been mentionedabove.

Deposition of metals or metal alloys on a plastics surface is generallycarried out in the context of plastics metallization, in particular inthe production of printed circuit boards.

In one particularly preferred embodiment of the processes of theinvention, the deposition of metals or metal alloys on metal or plasticssurfaces takes place in each case chemically or electrochemically. Suchprocesses are known to the skilled worker. With particular preference,the process of the invention comprises chemical or electrochemicaldeposition of gold, of copper or of nickel, chemical deposition ofpalladium, electrochemical deposition of zinc, and/or electrochemicaldeposition of tin. Said processes include not only the deposition of thespecified metals but also the deposition of their alloys with otherelements; particular preference is given here to CuZn, CuSn, CuNi, SnPb,SnAgBiCu, SnAgCu, SnBi, SnAg, SnCu, NiPd, NiP, ZnFe, ZnNi, ZnCo, ZnMn,said constituents of the alloy being present in the alloy in any desiredconcentration.

The invention also embraces processes where conductive polymers aredeposited, which in the widest sense are regarded as metals. One suchconductive polymer is polypyrrole.

Further embodiments of the process of the invention include, forexample, cleaning, etching, burnishing, and pickling processes, whereinnot only-is the component A used in accordance with the invention butalso, at the same time, acids, oxidizing agents and corrosioninhibitors, and dissolved metal salts are used, and also processes forthe production of printed circuit boards, in which compositionscomprising component A may be used not only for metallizing the circuitboard, including the vias present therein, but also for the surfacetreatment of the circuit board. Compositions comprising component A mayon the one hand be used in the surface treatment of metals present onthe circuit board, with the objective of corrosion protection, forinstance, or for improving the solderability, and also in processeswhere nonconducting surfaces are treated, as part of the metaldeposition process, with the compositions comprising component A thatare used in accordance with the invention, with the aim, for instance,of plating the through-holes of printed circuit boards.

In addition to the use of the polymer (component A) used in accordancewith the invention in the abovementioned processes, especially forpickling or passivating, especially for phosphating, metal surfaces orfor depositing metals on metal surfaces or plastics surfaces, it ispossible to add the polymers (component A) used in accordance with theinvention wherever corrosion protection is desired.

The present specification further provides for the use of polymers(component A) composed of

-   -   aa) at least one amino-containing polymer as component Aa,    -   ab) at least one aromatic compound as component Ab, being a        phenol or quinone or containing a phenolic or quinonoid        structural unit, and    -   ac) if desired, an aldehyde as component Ac        for the treatment of metal. The polymers (component A) are        preferably used for the corrosion inhibition of metal surfaces.

Polymers used with preference and also suitable metal surfaces andsuitable processes for corrosion inhibition and processes in which saidpolymers may be used have already been specified above.

A farther preferred utility relates to the use of polymers composed of

-   -   aa) at least one amino-containing polymer as component Aa,    -   ab) at least one aromatic compound as component Ab, being a        phenol or quinone or containing a phenolic or quinonoid        structural unit, and    -   ac) if desired, an aldehyde as component Ac        for the deposition of metals or metal alloys on a plastics        surface.

The polymers (component A) used in accordance with the inventioncomprise polymers obtained by reacting at least one amino-containingpolymer with an aromatic compound and, where appropriate, with analdehyde. Suitable amino-containing polymers are as already mentionedabove under component Aa, including polyvinylamine, polyvinyl-formamide,and polylysine, and also copolymers containing vinylamine,vinylformamide, and lysine as repeating units. The reaction products ofthese amino-containing polymers with an aromatic compound which is aphenol or quinone or contains a phenolic or quinonoid structural unit,especially-with benzoquinone in a Michael reaction (R1), or with phenolor pyrocatechol in the presence of an aldehyde in a Mannich reaction(R2), are not known from the prior art.

The present specification therefore further provides polymers composedof

-   -   a) at least one polymer or copolymer composed of at least one        repeating unit selected from the group consisting of vinylamine,        vinylformamide and lysine, as component A′a,    -   b) benzoquinone, phenol or pyrocatechol as component A′b, and    -   c) where appropriate, an aldehyde as component A′c.

Suitable aldehydes have already been listed above under component Ac.Suitable processes for preparing the polymers of the invention havelikewise already been set out above.

These polymers are especially suitable for use in the compositions ofthe invention and in the processes of the invention for the treatment ofmetal or plastics surfaces, preferably for the treatment of metalsurfaces, and for use for the treatment of metal or plastics surfaces,preferably for the corrosion inhibition of metal surfaces.

The examples which follow further illustrate the invention.

EXAMPLES Examples of the Preparation of Component A Examples A1-A3

To N1 parts of an aqueous polyvinylamine solution (polymer in deionizedform dissolved 11.15% in water, K value)* of the polymer: 36; preparedby hydrolysis of polyvinyl-formamide, degree of hydrolysis: 96.2%,corresponding to 243.5 mmol of amine per 100 g of polymer) there areadded N2 parts of pyrocatechol and subsequently N3 parts of 37% strengthaqueous formaldehyde solution. The reaction mixture is heated at 60° C.for 1 hour and after cooling is used as component A.

)* The K value is the Fikentscher constant for characterizing theaverage molecular weight; cf. H.-G. Elias, Makromoleküle vol. 1, 5thedition, Hüthig & Wepf Verlag, Basel 1990, page 99. Fraction Example A1Example A2 Example A3 N1 208.3 g 188.3 g 282.5 g N2  0.55 g 0.022 g0.003 g N3  0.41 g 0.016 g 0.002 g

Example A4

0.275 g of pyrocatechol is added to a solution of 32 g of polylysine in62.7 g of water. The reaction mixture is heated to 60-70° C, and 0.203 gof aqueous formaldehyde solution (37% by weight) is added. Aftercooling, the reaction product is used as component A.

Example A5

0.081 g of p-benzoquinone is introduced with cooling into a mixture of50 g of polyethyleneimine (Lupasol PR 8515 from BASF Aktiengesellschaft,Ludwigshafen am Rhein) and 100 g of water. The reaction product is usedas component A.

Examples A6-A9

0.083 g of pyrocatechol is introduced with cooling into a mixture of N4parts of polymer and 100 g of water. At room temperature, 0.203 g ofaqueous formaldehyde solution (37% by weight) is added and the mixtureis then heated to 60-70° C. After cooling, the reaction product is usedas component A. Example A6 Example A7 Example A8 Example A9 N4 150 g ofpolyethyleneimine 154 g of Mixture of 100 g of Mixture of 546 g (LupasolPR polyvinylamine poly(vinylamine- of polylysine and 8515 from BASFco-vinylformamide) 150 g of water Aktiengesellschaft, and 20 g ofpolyvinyl- Ludwigshafen am formamide Rhein)

Examples of Processes of the Invention Examples B1-B4

Steel panels coated electrolytically with zinc are treated with thefollowing formulations by immersion at 50° C. for 60 seconds: ExampleExample Example Example B1 B2 B3 B4 Reaction product 60 60 from exampleA1 Reaction product 50 from example A2 Reaction product 40 from exampleA6 MgCl₂ 8.5 Na acetate 45 8.5 Na formate 80 64 65% nitric acid 40 ml/lH₂SO₄ 5.5 H₃PO₄ 16 NaNO₃ 50 Formic acid 75 Acetic acid 16

The numbers in the table denote the concentrations of the respectivesubstances in water in g/l, unless indicated otherwise.

Examples B5-B8

The same as B1-B4 but using steel panels coated electrolytically withZnFe (10% by weight Fe content).

Example B9

Sheet aluminum is anodized at a current density of 15 A/dm² and 100° C.in a solution with the following composition:

-   -   H₃PO₄ 70% by weight, H₂SO₄ 10% by weight, HNO₃ 4% by weight,        boric acid 0.5% by weight, NH₅F₂ 16% by weight, reaction product        from example (A2) 9.5% by weight.

Example B10

Cast iron is immersed for 15 seconds at room temperature in a solutionof 10% of H₂SO₄ and 30% by weight of the reaction product from exampleA5.

Example B 11

100 g of a polymer dispersion (30% solids content, composed of acopolymer with the composition 47% by weight n-butyl acrylate, 50% byweight styrene, 3% by weight acrylic acid) are mixed with 100 g of waterand 2 g of the reaction product from example A1 and used for coating azincked steel panel passivated with HNO₃ (0.05% by weight).

Example B12 Electrochemical Deposition of Zinc Alloy

For the electrochemical deposition of an alloy coat comprising zinc anda further metal M at 40° C. and a current density of 1.5 A/dm²,electroplating baths with the following composition are used.  10 g/lzinc, as zinc oxide  2 g/l metal M, as sulfate 100 g/l sodium hydroxide 15 g/l carboxymethylated polyethyleneimine, Na salt, from example 1  5g/l polyethyleneimine Lugalvan ® G20 from BASF Aktiengesellschaft,Ludwigshafen/Rhein  5 g/l reaction product from example A3  1 g/lpyridinium propylsulfobetaine

The metal M is optionally cobalt, iron, nickel or manganese.

Performance tests B1-B12

The products of examples B1 to B 11 are salt spray tested and havedurability times which are 5-30% higher than in the case of comparableprocesses in which the polymers C are not employed.

Platelet Test

1 g of each of compounds Al to A9 are introduced into 99 g of 0.04 molaraqueous NaCl solution. Steel (1.0037) platelets of known mass are placedin the solution and kept therein for 7 days. The platelets are thenfreed from adhering rust, rinsed, dried and weighed. The inhibitionefficiency of the substances A1 to A9 is calculated from the mass lossΔm_(sample) on storage relative to the mass loss on storage withoutinhibitor, Δm₀, as follows:E=(Δm ₀ −Δm _(Probe))/Δm₀

For compounds A1 to A9, E is 5-50%.

Phosphating Test

Each of the substances Al to A9 is used as test substance in thefollowing test:

-   -   phosphating solution A: 25 g of phosphoric acid (85%), 10 g of        Na acetate, 5 g of test substance, 960 g of water    -   phosphating solution B: 25 g of phosphoric acid (85%), 10 g of        Na acetate, 15 g of test substance, 950 g of water    -   phosphating solution C: 25 g of phosphoric acid (85%), 10 g of        Na acetate, 45 g of test substance, 920 g water phosphating        solution D (comparative experiment): 25 g of phosphoric acid        (85%), 10 g of Na acetate, 965 g of water

In each case 7 steel panels are treated as follows: (1) clean steelpanel//(2) rinse under running water (20 seconds)//(3) immerse inphosphating solution at 90° C.//(4) rinse under running water (20seconds)//(5) blow dry//(6) store in air (23° C., 50% humidity) for 1week.

-   -   Panel 1: 1 minute in solution A    -   Panel 2: 25 minutes in solution A    -   Panel 3: 5 minutes in solution B    -   Panel 4: 1 minute in solution C    -   Panel 5: 25 minutes in solution C    -   Panel 6: 1 minute in solution D    -   Panel 7: 25 minutes in solution D

For all substances A1 to A9, the panels 1-5 exhibit significantly lessrust than panels 6 and 7.

1-12. (canceled)
 13. A composition for the treatment of metal surfacesor for the deposition of metal or metal alloys on plastics surfaces,comprising b) water or another solvent suitable for dissolving,dispersing, suspending or emulsifying the polymer (component A), ascomponent B; c) if desired, surface-active compounds, dispersants,suspension media and/or emulsifiers as component C wherein thecomposition comprises a) at least one polymer as component A, composedby reaction of aa) at least one amino-containing polymer as componentAa; ab) at least one aromatic compound as component Ab, being a phenolor quinone or containing a phenolic or quinonoid structural unit; ac) ifdesired, an aldehyde as component Ac.
 14. A composition as claimed inclaim 13, for the treatment of metal surfaces comprising further tocomponents A, B and, where appropriate, C d) at least one salt, acid orbase based on transition metal cations, transition metal oxo anions,fluorometallates or lanthanoids as component D, and/or e) at least oneacid selected from the group consisting of phosphoric acid, sulfuricacid, sulfonic acids, nitric acid, hydrofluoric acid, and hydrochloricacid, as component E.
 15. Composition as claimed in claim 14, comprisingf) at least one further corrosion inhibitor as component F, and/or g)compounds of Ce, Ni, Co, V, Fe, Zn, Zr, Ca, Mn, Mo, W, Cr and/or Bi ascomponent G, and/or h) further auxiliaries and additives as component H.16. A composition for the treatment of metal surfaces or for thedeposition of metal or metal alloys on plastics surfaces as claimed inclaim 13, comprising further to components A, B and, where appropriate,C: i) at least one metal oxide and/or metal salt as component I, j)where appropriate, at least one complexing agent as component J.
 17. Thecomposition as claimed in claim 16, comprising k) where appropriate, atleast one acid or an alkali metal salt or alkaline earth metal salt ofthe corresponding acid, as component K, and l) where appropriate,further additions as component L.
 18. A process for the treatment of ametal surface, which comprises contacting the metal surface with apolymer (component A) composed by reaction of aa) at least oneamino-containing polymer as component Aa, ab) at least one aromaticcompound as component Ab, being a phenol or quinone or containing aphenolic or quinonoid structural unit, and ac) if desired, an aldehydeas component Ac.
 19. A process for the treatment of a metal surface,which comprises contacting the metal surface with a composition asclaimed in claim
 13. 20. A process as claimed in claim 17, comprisingthe steps of: a) where appropriate, cleaning the metal surface to removeoils, fats, and dirt, b) where appropriate, washing with water, c) whereappropriate, pickling to remove rust or other oxides, in the presence orabsence of the polymer (component A), d) where appropriate, washing withwater, e) treatment of the metal surface in the presence of the polymer(component A).
 21. A process as claimed in claim 20, additionallycomprising the steps of f) where appropriate, washing with water, g)where appropriate, aftertreatment, in the presence or absence of thepolymer (component A).
 22. A composition as claimed in claim 13, whereinthe amino-containing polymer is selected from the group consisting ofpolyethyleneimine, polyvinylamine, poly(vinylformamid-co-vinylamine),polylysine, polyaminostyrene, amino-containing derivatives ofpolycarboxylates, reaction products of polyamines with carboxylic acidsand/or sulfonic acids, and carboxymethylation products of polyamines.